Efficient non-resonant intermolecular vibrational energy transfer

Abstract

Molecular excited vibrational states are metastable states and we incorporate their finite lifetimes into the theory of vibrational energy transfer between weakly interacting molecules, i.e., at internuclear distances at which they do not have a chemical bond. Expressions for the effective lifetime of an initially vibrationally excited molecule in the presence of a neighbouring molecule are derived in closed form. These expressions allow one to analyse the physics behind the energy transfer. It is shown that due to different finite lifetimes of the isolated excited molecules, a very efficient vibrational energy transfer can take place between them even if their energies are rather off-resonance. Examples are discussed.